CN115141357B - Water-oil universal epoxy curing agent and preparation method thereof - Google Patents
Water-oil universal epoxy curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN115141357B CN115141357B CN202210883121.XA CN202210883121A CN115141357B CN 115141357 B CN115141357 B CN 115141357B CN 202210883121 A CN202210883121 A CN 202210883121A CN 115141357 B CN115141357 B CN 115141357B
- Authority
- CN
- China
- Prior art keywords
- water
- curing agent
- epoxy
- oil
- epoxy curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 79
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 11
- -1 phenolic amide Chemical class 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 24
- 150000001412 amines Chemical class 0.000 claims description 21
- 244000226021 Anacardium occidentale Species 0.000 claims description 16
- 235000020226 cashew nut Nutrition 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 12
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 12
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 12
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 239000004848 polyfunctional curative Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000010276 construction Methods 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 239000003125 aqueous solvent Substances 0.000 abstract description 2
- 239000012897 dilution medium Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 34
- 238000012360 testing method Methods 0.000 description 19
- 239000003973 paint Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 238000010790 dilution Methods 0.000 description 8
- 239000012895 dilution Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229920006334 epoxy coating Polymers 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 231100000206 health hazard Toxicity 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/64—Amino alcohols
Abstract
The invention discloses a water-oil universal epoxy curing agent and a preparation method thereof, belonging to the field of high polymer materials. The water-oil universal epoxy curing agent has compatibility of different solvent environments, can be diluted and stably stored in an aqueous solvent and an organic solvent, so that a proper dilution medium can be selected according to the actual construction environment in the construction process, the difference of construction and subsequent coating effects can not be caused, and the application range is remarkably expanded. The product is environment-friendly, and has excellent corrosion resistance, mechanical property and chemical resistance. The invention also discloses a preparation method of the water-oil universal epoxy curing agent.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a water-oil universal epoxy curing agent and a preparation method thereof.
Background
The epoxy resin can be subjected to crosslinking reaction with various curing agents to form a polymer with excellent performance, and the polymer has excellent insulating performance, mechanical and physical properties, chemical corrosion resistance, wet heat resistance, adhesive property and the like, and is widely used in the fields of coating, molding materials, adhesives and the like. The epoxy resin is convenient to cure, the process is simple, excessive pressure is not required to be applied, and the epoxy resin and the epoxy curing agent form a common epoxy coating system. The epoxy paint currently on the market mainly includes solvent-type epoxy paint cured using a solvent-type epoxy curing agent and water-based epoxy paint cured using a water-based epoxy curing agent. The solvent type epoxy curing agent has the main advantages of low requirements on brushing conditions, wide construction temperature and humidity range and high viscosity, so that flowing and sagging phenomena are not easy to occur in the construction process, the leveling property is good, and a paint film is smooth; in addition, the solvent-type epoxy coating has the advantages of strong permeability, excellent adhesion of the base material, bright and attractive luster and the like. However, the solvent type epoxy curing agent used by the epoxy curing agent contains more volatile organic solvents, so that the VOC content is higher during use, and the health hazard and the environmental pollution are caused. In contrast, the waterborne epoxy coating cured by the waterborne curing agent has the advantages of extremely low VOC, less harmful gas, safe construction, clean water washing, environmental friendliness and the like, is an important development direction of the current coating industry, but has higher requirements on construction environment, construction temperature of more than 5 ℃ and limited application range. In addition, too high humidity in the construction environment may affect the evaporation of water in the coating system, resulting in poor coating film hardness, poor substrate adhesion, poor gloss, and other adverse effects.
Although the construction unit can switch to and fro to use solvent type epoxy paint (i.e. oily paint) or water type epoxy paint according to the construction environment, the switching can cause non-uniform construction and seriously affect the uniformity and stability of the coating film. The property of the epoxy paint is mainly determined by the curing agent used by the epoxy paint, so that the development of the water-oil universal epoxy curing agent which is green and environment-friendly, wide in application range and good in use effect is a strong demand in the current market.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the water-oil universal epoxy curing agent which can be respectively diluted and stably stored in a water solvent system or an organic solvent system, and can keep the same dilutability under different solvent systems, and a construction unit can perform construction by selecting different dilution solvents according to actual environments without causing the difference in construction and subsequent coating effects; the product is environment-friendly, and has excellent mechanical property and chemical resistance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a general epoxy curing agent for water and oil has the molecular structure as follows:
wherein R is alkyl, n1=1 to 4, n2=5 to 100, and n3=3 to 10.
Preferably, the viscosity of the water-oil universal epoxy hardener is 1000-4000 cps at 25 ℃, and the amine value is 300-360 mgKOH/g.
The invention also aims to provide a preparation method of the water-oil universal epoxy curing agent, which comprises the following steps:
mixing and stirring cashew phenol aldehyde amide, polyethylene glycol epoxy adduct and polyether amine for 25-35 min, heating to 60-120 ℃ and continuously stirring for 1.8-2.2 h, then adding epoxy resin, keeping warm and stirring for 25-35 min, and cooling to obtain the water-oil universal epoxy curing agent.
The preparation method of the water-oil universal epoxy curing agent is simple, has low equipment requirement, and can realize industrial mass production.
Preferably, the viscosity of the cashew phenolic amide is 500-1500 cps at 25 ℃, and the amine value is 360-420 mgKOH/g.
Preferably, the preparation method of the cashew phenol formaldehyde amide comprises the following steps:
uniformly mixing cardanol epoxide and polyamine, heating to 90-130 ℃ for reaction for 1.8-2.2 h, adding dibasic acid, uniformly mixing, continuously heating to 165-200 ℃ for reaction for 1.8-2.2 h, preserving the temperature of the obtained mixture, and distilling under reduced pressure for 25-35 min to obtain the cardanol phenolic amide.
More preferably, the cardanol epoxide has a molecular structure of:
the polyamine is at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamine and polyether amine;
the dibasic acid is dibasic fatty acid, more preferably at least one of suberic acid, sebacic acid and dimer acid.
Preferably, the molecular structure of the polyethylene glycol epoxy adduct is:
wherein n=5 to 100.
Preferably, the epoxy resin is bisphenol A epoxy resin, and the epoxy equivalent is 180-250.
Preferably, the solid content of the water-oil universal epoxy curing agent prepared by the preparation method of the water-oil universal epoxy curing agent is more than or equal to 98.5%.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a water-oil universal epoxy curing agent, which has compatibility of different solvent environments, can be diluted and stably stored in an aqueous solvent and an organic solvent, so that a proper dilution medium can be selected according to the actual construction environment in the construction process, the difference of construction and subsequent coating effects can not be caused, and the application range is obviously enlarged. The product is environment-friendly, and has excellent corrosion resistance, mechanical property and chemical resistance. The invention also provides a preparation method of the water-oil universal epoxy curing agent.
Drawings
FIG. 1 is an infrared analysis spectrum of the water-oil universal epoxy hardener of example 1 of the present invention;
FIG. 2 is an infrared analysis spectrum of the water-oil universal epoxy hardener of example 2 of the present invention;
FIG. 3 is an infrared analysis spectrum of the water-oil universal epoxy hardener of example 3 of the present invention;
FIG. 4 is a schematic diagram showing the results of the product in effect example 1 of the present invention after salt spray resistance test, wherein a is the result of the product after 500h salt spray resistance test after 24h room temperature curing of cold-rolled steel sheet with rough surface; b is the result of the salt spray resistance test of the product after 7d of curing at room temperature of the frosted steel plate for 800 hours; c is the result of the salt spray resistance test of 1500 hours after the product is baked at 80 ℃ for 1 hour and solidified;
FIG. 5 is a graph showing the results of chemical resistance test of the product of effect example 1 according to the present invention, wherein a is a graph showing the results of immersing the product in deionized water; b is a graph of the result of the product after being soaked in 50% NaOH aqueous solution; c is a result graph of the product after being soaked in ethanol; d is a result graph of the product after being soaked in crude oil; e is a result graph of the product after being soaked in dimethylbenzene;
FIG. 6 is a graph showing the results of the adhesion test of the product of effect example 1 of the present invention, wherein a is a graph showing the results of the adhesion of the product to a smooth cold-rolled steel sheet; b is a result graph of the adhesion of the product on the galvanized steel sheet; c is a result graph of the adhesion of the product on the aluminum alloy plate;
FIG. 7 is a dilution graph showing the dilution performance test of the product of effect example 1 of the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples. It is intended that the invention be interpreted in detail and not as a limitation. All other embodiments, which can be made by those skilled in the art without the inventive effort, are intended to be within the scope of the present invention. The experimental reagents and instruments involved in the practice of the present invention are common reagents and instruments unless otherwise specified.
Example 1
The invention relates to a water-oil universal epoxy curing agent and an embodiment of a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Preparation of cashew phenolic amide:
615g of cardanol epoxide is added into a 2L glass reaction bottle with a reflux condenser tube and a temperature controller, 425g of diethylenetriamine is slowly added under the stirring condition and is stirred for 30min at the rotation speed of 250rpm, the temperature is raised to 120 ℃ for reflux and stirring for 2h, 450g of dimer acid is added for uniform mixing and is continuously raised to 195 ℃ for normal pressure reaction for 2h, and the obtained mixture is subjected to heat preservation and reduced pressure vacuum distillation and dehydration for 30min to obtain light yellow cashew phenolic amide; the viscosity of the material at 25 ℃ is 500-1500 cps, and the amine value is 360-420 mgKOH/g.
The molecular structure of the cardanol epoxide is as follows:
(2) Preparation of a water-oil universal epoxy curing agent:
mixing cashew phenolic amide with 492g of polyethylene glycol epoxy adduct and 250g of polyether amine (commercial D230 type polyether amine) under stirring for 30min, heating to 100 ℃ and continuing stirring for 2h, then adding 344g of epoxy resin (commercial E51 type epoxy resin, the epoxy equivalent is 190), carrying out heat preservation and stirring for 30min, and cooling to obtain a light yellow general-purpose epoxy curing agent for water and oil; the viscosity of the material at 25 ℃ is 1000-4000 cps, the amine value is 300-360 mgKOH/g, and the solid content is 98.9%;
the molecular structure of the polyethylene glycol epoxy adduct is as follows:
wherein n=5 to 100.
The obtained water-oil universal epoxy curing agent is subjected to infrared analysis, and the test result is shown in figure 1.
As can be seen from FIG. 1, at 3360.59cm -1 The wider band is the stretching vibration peak of hydroxyl and the stretching vibration peak of N-H bond; located at 2923.04cm -1 The peak average of (2) is the stretching vibration peak of C-H bond on methylene; located at 1646.89cm -1 The peak of (2) is the stretching vibration peak of the amide bond; located at 1606.50cm -1 、1509.45cm -1 And 1457.77cm -1 The nearby peak is a benzene ring framework stretching vibration peak; located at 1249.52cm -1 The peak of (2) is the stretching vibration peak of aromatic ether bond; located at 1099.12cm -1 The peak of (2) is a stretching vibration peak of ether bond. The characteristic peaks show that the actual synthetic reaction route of the product accords with the expected one and corresponds to the molecular structure matching of the water-oil universal epoxy curing agent.
Example 2
The invention relates to a water-oil universal epoxy curing agent and an embodiment of a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Preparation of cashew phenolic amide:
615g of cardanol epoxide is added into a 2L glass reaction bottle with a reflux condenser tube and a temperature controller, 250g of diethylenetriamine, 210g of triethylenetetramine and 10g of tetraethylenepentamine are slowly added under the stirring condition and are stirred for 30min at the rotating speed of 250rpm, the temperature is increased to 120 ℃ for reflux stirring for 2h, 450g of dimer acid is added for uniform mixing and is continuously increased to 195 ℃ for normal pressure reaction for 2h, and the obtained mixture is subjected to heat preservation and vacuum distillation and dehydration for 30min under reduced pressure, so as to obtain light yellow cashew phenolic amide; the viscosity of the material at 25 ℃ is 500-1500 cps, and the amine value is 360-420 mgKOH/g.
The molecular structure of the cardanol epoxide is as follows:
(2) Preparation of a water-oil universal epoxy curing agent:
mixing cashew phenolic amide with 492g of polyethylene glycol epoxy adduct and 250g of polyether amine (commercial D230 type polyether amine) under stirring for 30min, heating to 100 ℃ and continuing stirring for 2h, then adding 344g of epoxy resin (commercial E51 type epoxy resin, the epoxy equivalent is 190), carrying out heat preservation and stirring for 30min, and cooling to obtain a light yellow general-purpose epoxy curing agent for water and oil; the viscosity of the material at 25 ℃ is 1000-4000 cps, the amine value is 300-360 mgKOH/g, and the solid content is 99.1%;
the molecular structure of the polyethylene glycol epoxy adduct is as follows:
wherein n=5 to 100;
the obtained water-oil universal epoxy hardener was subjected to infrared analysis, and the test results are shown in fig. 2.
As can be seen from FIG. 2, at 3360.97cm -1 The wider band is the stretching vibration peak of hydroxyl and the stretching vibration peak of N-H bond; located at 2924.37cm -1 、2854.94cm -1 The peak average of (2) is the stretching vibration peak of C-H bond on methylene; located at 1644.58cm -1 The peak of (2) is the stretching vibration peak of the amide bond;located at 1581.58cm -1 、1508.75cm -1 And 1459.80cm -1 The nearby peak is a benzene ring framework stretching vibration peak; located at 1298.69cm -1 The peak of (2) is the stretching vibration peak of aromatic ether bond; located at 1099.94cm -1 The peak of (2) is a stretching vibration peak of ether bond. The characteristic peaks show that the actual synthetic reaction route of the product accords with the expected one and corresponds to the molecular structure matching of the water-oil universal epoxy curing agent.
Example 3
The invention relates to a water-oil universal epoxy curing agent and an embodiment of a preparation method thereof, wherein the preparation method comprises the following steps:
(1) Preparation of cashew phenolic amide:
615g of cardanol epoxide is added into a 2L glass reaction bottle with a reflux condenser tube and a temperature controller, 540g of triethylene tetramine and 10g of tetraethylene pentamine are slowly added under the stirring condition and are stirred for 30min at the rotating speed of 250rpm, the temperature is increased to 120 ℃ for reflux and stirring for 2h, 162g of sebacic acid is added for uniform mixing and is continuously heated to 195 ℃ for normal pressure reaction for 2h, and the obtained mixture is subjected to heat preservation, reduced pressure, vacuum distillation and dehydration for 30min to obtain light yellow cashew phenolic amide; the viscosity of the material at 25 ℃ is 500-1500 cps, and the amine value is 360-420 mgKOH/g.
The molecular structure of the cardanol epoxide is as follows:
(2) Preparation of a water-oil universal epoxy curing agent:
mixing cashew phenolic amide with 492g of polyethylene glycol epoxy adduct and 250g of polyether amine (commercial D230 type polyether amine) under stirring for 30min, heating to 100 ℃ and continuing stirring for 2h, then adding 398g of epoxy resin (commercial E44 type epoxy resin, the epoxy equivalent is 220), carrying out heat preservation and stirring for 30min, and cooling to obtain a light yellow general-purpose epoxy curing agent for water and oil; the viscosity of the material at 25 ℃ is 1000-4000 cps, the amine value is 300-360 mgKOH/g, and the solid content is 98.8%;
the molecular structure of the polyethylene glycol epoxy adduct is as follows:
wherein n=5 to 100;
the obtained water-oil universal epoxy hardener was subjected to infrared analysis, and the test results are shown in fig. 3.
As can be seen from FIG. 3, at 3360.17cm -1 The wider band is the stretching vibration peak of hydroxyl and the stretching vibration peak of N-H bond; located at 2924.41cm -1 、2854.96cm -1 The peak average of (2) is the stretching vibration peak of C-H bond on methylene; located at 1645.35cm -1 The peak of (2) is the stretching vibration peak of the amide bond; located at 1606.03cm -1 、1508.82cm -1 And 1459.39cm -1 The nearby peak is a benzene ring framework stretching vibration peak; located at 1298.58cm -1 The peak of (2) is the stretching vibration peak of aromatic ether bond; located at 1099.60cm -1 The peak of (2) is a stretching vibration peak of ether bond. The characteristic peaks show that the actual synthetic reaction route of the product accords with the expected one and corresponds to the molecular structure matching of the water-oil universal epoxy curing agent.
Effect example 1
In order to verify the use effect of the water-oil universal epoxy curing agent, the product obtained in the example 1 is subjected to salt spray test, chemical resistance test, adhesive force test and dilution capability test.
Wherein, salt spray test is carried out according to ASTM B117-2007 standard, after the products are formed into films on different base materials, the films are placed in a salt spray tester, and whether the appearance of the paint film has the phenomena of bubbles, flaking and the like is observed, and the results are shown in Table 1 and FIG. 4. It can be seen that when the product is used on different base materials, the salt spray resistance of the product is excellent, and obvious bubble and peeling phenomena are avoided.
TABLE 1
| Test item (coating thickness 50-60 μm) | Performance results |
| Frosted cold-rolled steel plate for 24h room temperature solidification | 500hr, no bubble, flaking, etc |
| Frosted steel plate is solidified at room temperature for 7 days | 800hr, no bubble, flaking, etc |
| Baking the frosted steel plate at 80 ℃ for 1h | 1500hr, no bubble, flaking, etc |
The chemical resistance test is carried out according to the GB/T9274-1988 standard, after the product is solidified into a film, the film is soaked in different chemical varieties respectively, whether the appearance of the film appears, and the phenomena of whitening, foaming, softening and flaking are observed, and the results are shown in the table 2 and figure 5. As can be seen from the table and the graph, the water-oil universal epoxy curing agent can resist the erosion of various solvents after curing, has no obvious change in appearance, does not have the phenomena of blushing, foaming, softening or flaking, and has excellent chemical resistance.
TABLE 2
| Chemical product | Paint film appearance (GB/T9274-1988) |
| Deionized water | No blushing and onset of actionBubble, softening, flaking, etc |
| 50% aqueous NaOH solution | Has no blushing, foaming, softening, flaking, etc |
| Ethanol | Has no blushing, foaming, softening, flaking, etc |
| Crude oil | Has no blushing, foaming, softening, flaking, etc |
| Xylene (P) | Has no blushing, foaming, softening, flaking, etc |
Adhesion test the adhesion of the product on different substrates was tested according to astm d3359-B standard and the results are shown in table 3 and fig. 6. From the results, the product of the invention shows excellent adhesive force effect on different use substrates.
TABLE 3 Table 3
| Performance test items (film thickness 35 μm) | Performance parameters (ASTMD 3359-B) |
| Smooth cold-rolled steel plate is cured for 7 days at room temperature | 5B |
| Galvanized steel sheet is cured for 7 days at room temperature | 5B |
| Aluminum alloy plate is cured for 7 days at room temperature | 5B |
The dilution ability test was carried out by respectively diluting propylene glycol methyl ether, xylene and water in different dilution ratios, and testing the viscosity number (25 ℃) according to ASTM D2196, and the results are shown in Table 4 and FIG. 7. As can be seen from FIG. 7, the water-oil universal epoxy hardener of the invention has similar dilution performance under different solvents, and the viscosity change trend of the product under different solvents is almost the same along with the increase of dilution ratio, which indicates that the product can be applied to different solvent environments.
TABLE 4 Table 4
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The general epoxy curing agent for water and oil is characterized by comprising the following molecular structures:
；
wherein R is alkyl, n1=1 to 4, n2=5 to 100, n3=3 to 10;
the preparation method of the water-oil universal epoxy curing agent comprises the following steps:
mixing and stirring cashew phenolic amide, polyethylene glycol epoxy adduct and polyether amine for 25-35 min, heating to 60-120 ℃, continuously stirring for 1.8-2.2 h, then adding epoxy resin, carrying out heat preservation and stirring for 25-35 min, and cooling to obtain the water-oil universal epoxy curing agent.
2. The water-oil type epoxy hardener of claim 1, wherein the viscosity of the water-oil type epoxy hardener is 1000 to 4000cps at 25 ℃ and the amine value is 300 to 360mgkoh/g.
3. The method for preparing the water-oil universal epoxy curing agent as claimed in claim 1 or 2, comprising the following steps:
mixing and stirring cashew phenolic amide, polyethylene glycol epoxy adduct and polyether amine for 25-35 min, heating to 60-120 ℃, continuously stirring for 1.8-2.2 h, then adding epoxy resin, carrying out heat preservation and stirring for 25-35 min, and cooling to obtain the water-oil universal epoxy curing agent.
4. The method for preparing the water-oil universal epoxy curing agent according to claim 3, wherein the viscosity of the cashew phenolic amide is 500-1500 cps at 25 ℃, and the amine value is 360-420 mgKOH/g.
5. The method for preparing the water-oil universal epoxy curing agent according to claim 4, wherein the method for preparing the cashew phenol formaldehyde amide comprises the following steps:
uniformly mixing cardanol epoxide and polyamine, heating to 90-130 ℃ for reaction for 1.8-2.2 h, adding dibasic acid, uniformly mixing, continuously heating to 165-200 ℃ for reaction for 1.8-2.2 h, preserving the temperature of the obtained mixture, and distilling under reduced pressure for 25-35 min to obtain the cardanol phenolic amide.
6. The method for preparing the water-oil universal epoxy hardener of claim 5, wherein the cardanol epoxide has a molecular structure as follows:
；
the polyamine is at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethylene polyamine and polyether amine;
the dibasic acid is at least one of suberic acid, sebacic acid and dimer acid.
7. The method for preparing the water-oil universal epoxy hardener of claim 3, wherein the molecular structure of the polyethylene glycol epoxy adduct is:
；
wherein n=5 to 100.
8. The method for preparing a water-oil universal epoxy curing agent according to claim 3, wherein the epoxy resin is bisphenol A epoxy resin, and the epoxy equivalent is 180-250.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210883121.XA CN115141357B (en) | 2022-07-26 | 2022-07-26 | Water-oil universal epoxy curing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210883121.XA CN115141357B (en) | 2022-07-26 | 2022-07-26 | Water-oil universal epoxy curing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115141357A CN115141357A (en) | 2022-10-04 |
| CN115141357B true CN115141357B (en) | 2024-03-08 |
Family
ID=83415083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210883121.XA Active CN115141357B (en) | 2022-07-26 | 2022-07-26 | Water-oil universal epoxy curing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115141357B (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995012146A1 (en) * | 1993-10-26 | 1995-05-04 | Toray Industries, Inc. | Dry lithographic forme |
| KR100559055B1 (en) * | 2004-12-30 | 2006-03-10 | 주식회사 디피아이 | Cardanol-modified epoxy resin composition |
| EP1873181A2 (en) * | 2006-06-29 | 2008-01-02 | Air Products and Chemicals, Inc. | Curing agent for epoxy resin and coating composition |
| WO2010121397A1 (en) * | 2009-04-23 | 2010-10-28 | 广州秀珀化工股份有限公司 | Water-soluble epoxy curing agent and method for preparing the same |
| CN102977670A (en) * | 2012-11-15 | 2013-03-20 | 江苏三木化工股份有限公司 | Cashew phenolic aldehyde amide epoxy hardener for four-season-general type anticorrosive paint and preparation method of cashew phenolic aldehyde amide epoxy hardener |
| CN109517141A (en) * | 2018-10-11 | 2019-03-26 | 安徽大学 | A kind of modified by cardanol aqueous epoxy curing agent and preparation method thereof |
| CN113061233A (en) * | 2021-03-05 | 2021-07-02 | 卡德莱化工(珠海)有限公司 | Waterborne emulsion epoxy curing agent and preparation method and application thereof |
| CN113072686A (en) * | 2021-05-06 | 2021-07-06 | 上海经天新材料科技有限公司 | Preparation method of aldehyde-free waterborne cardanol ketone amine epoxy curing agent |
| CN113788934A (en) * | 2021-08-30 | 2021-12-14 | 南京嘉钺生物科技有限公司 | Water-soluble self-emulsifying phenolic aldehyde modified amine water-based epoxy curing agent and preparation method thereof |
| CN114524917A (en) * | 2022-02-18 | 2022-05-24 | 浙江万盛股份有限公司 | Preparation method of water-based cardanol modified polyamine curing agent |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL3784714T3 (en) * | 2018-04-26 | 2023-07-17 | Elantas Beck India Ltd. | Cardanol based curing agent for epoxy resins compositions |
| CN110066383B (en) * | 2019-04-18 | 2020-05-08 | 万华化学集团股份有限公司 | Ionic waterborne epoxy curing agent and preparation method and application thereof |
| CN111763151B (en) * | 2020-06-29 | 2021-11-30 | 浙江万盛股份有限公司 | Preparation method of cardanol modified polyamine curing agent with high corrosion resistance |
-
2022
- 2022-07-26 CN CN202210883121.XA patent/CN115141357B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995012146A1 (en) * | 1993-10-26 | 1995-05-04 | Toray Industries, Inc. | Dry lithographic forme |
| KR100559055B1 (en) * | 2004-12-30 | 2006-03-10 | 주식회사 디피아이 | Cardanol-modified epoxy resin composition |
| EP1873181A2 (en) * | 2006-06-29 | 2008-01-02 | Air Products and Chemicals, Inc. | Curing agent for epoxy resin and coating composition |
| WO2010121397A1 (en) * | 2009-04-23 | 2010-10-28 | 广州秀珀化工股份有限公司 | Water-soluble epoxy curing agent and method for preparing the same |
| CN102977670A (en) * | 2012-11-15 | 2013-03-20 | 江苏三木化工股份有限公司 | Cashew phenolic aldehyde amide epoxy hardener for four-season-general type anticorrosive paint and preparation method of cashew phenolic aldehyde amide epoxy hardener |
| CN109517141A (en) * | 2018-10-11 | 2019-03-26 | 安徽大学 | A kind of modified by cardanol aqueous epoxy curing agent and preparation method thereof |
| CN113061233A (en) * | 2021-03-05 | 2021-07-02 | 卡德莱化工(珠海)有限公司 | Waterborne emulsion epoxy curing agent and preparation method and application thereof |
| CN113072686A (en) * | 2021-05-06 | 2021-07-06 | 上海经天新材料科技有限公司 | Preparation method of aldehyde-free waterborne cardanol ketone amine epoxy curing agent |
| CN113788934A (en) * | 2021-08-30 | 2021-12-14 | 南京嘉钺生物科技有限公司 | Water-soluble self-emulsifying phenolic aldehyde modified amine water-based epoxy curing agent and preparation method thereof |
| CN114524917A (en) * | 2022-02-18 | 2022-05-24 | 浙江万盛股份有限公司 | Preparation method of water-based cardanol modified polyamine curing agent |
Non-Patent Citations (3)
| Title |
|---|
| 无溶剂环氧防腐涂料的制备和性能研究;郭超群;张超灿;;现代涂料与涂装(06);全文 * |
| 水性环氧树脂固化剂的研究进展;王思学;杨建军;吴庆云;吴明元;张建安;;涂料工业(08);全文 * |
| 环氧树脂腰果酚醛胺及腰果酚醛酰胺固化剂的合成及其性能研究;邱国栋;钱阳;朱斌;朱爱萍;;涂料工业(08);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115141357A (en) | 2022-10-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3008848A (en) | Adhesive resin primer composition, method of bonding a synthetic resin to a base therewith and article produced thereby | |
| CN102939314A (en) | Use of cyclic carbonates in epoxy resin compositions | |
| CN110760234A (en) | Preparation method of wear-resistant, heat-insulating and corrosion-resistant powder coating | |
| CN115141357B (en) | Water-oil universal epoxy curing agent and preparation method thereof | |
| CN111732872A (en) | Preparation method of urushiol-based environment-friendly wood wax oil | |
| CN102746786B (en) | Ultraviolet-light-cured elastic top varnish and production method thereof | |
| EP0156437A1 (en) | A liquid coating composition, a method of coating a metal substrate and the metal substrate thus obtained | |
| CN113061233A (en) | Waterborne emulsion epoxy curing agent and preparation method and application thereof | |
| CN112341605A (en) | Preparation method of waterborne orange peel epoxy curing agent and flat coating agent used in cooperation with waterborne orange peel epoxy curing agent | |
| NL2031236B1 (en) | Tung oil-based modified amine curing agent and preparation method and use thereof | |
| US4769420A (en) | Binder which is rendered water-dilutable by protonation with an acid, from carboxyl terminated butadiene/acrylonitrile copolymers | |
| CN110982376A (en) | Anti-skid powder coating and online coating method thereof | |
| US3075932A (en) | Process for curing polyepoxides with polyamino polyamide compounds and resulting products | |
| JPH02276876A (en) | Aqueous resin composition | |
| US3261882A (en) | Adhesives from polyisophthalamides and thermosetting epoxy resin syrups | |
| CN112724803B (en) | Plane powder coating composition and coating thereof | |
| JPH0689275B2 (en) | Coating composition | |
| KR20070070882A (en) | Anticorrosive paint composition comprising mannich hardener and polyamide adduct hardener | |
| CN113788934A (en) | Water-soluble self-emulsifying phenolic aldehyde modified amine water-based epoxy curing agent and preparation method thereof | |
| CN110951341A (en) | Automobile finish composite coating capable of being rapidly cured and long in activation period and preparation method thereof | |
| CN110862753A (en) | Sealing primer capable of sealing organic acid and pigment of wood and preparation method thereof | |
| CN114350225B (en) | Microgel for cathode electrophoretic coating and preparation method thereof | |
| CN111718473B (en) | Ionic waterborne epoxy modified curing agent and preparation method thereof | |
| CN110819178A (en) | Environment-friendly coating, preparation method, application and use method | |
| CN111423560A (en) | Hydroxyl curing type epoxy resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |